Nano-imprint lithography of broad-band and wide-angle antireflective structures for high-power lasers.

We demonstrate efficient anti reflection coatings based on adiabatic index matching obtained via nano-imprint lithography. They exhibit high total transmission, achromaticity (99.5% < T < 99.8% from 390 to 900 nm and 99% < T < 99.5% from 800 to 1600 nm) and wide angular acceptance (T > 99% up to 50 degrees). Our devices show high laser-induced damage thresholds in the sub-picosecond (>5 J/cm2 at 1030 nm, 500 fs), nanosecond (>150 J/cm2 at 1064 nm, 12 ns and >100 J/cm2 at 532 nm, 12 ns) regimes, and low absorption in the CW regime (<1.3 ppm at 1080 nm), close to those of the fused silica substrate.

Back-propagation optimization and multi-valued artificial neural networks for highly vivid structural color filter metasurfaces.

We introduce a novel technique for designing color filter metasurfaces using a data-driven approach based on deep learning. Our innovative approach employs inverse design principles to identify highly efficient designs that outperform all the configurations in the dataset, which consists of 585 distinct geometries solely. By combining Multi-Valued Artificial Neural Networks and back-propagation optimization, we overcome the limitations of previous approaches, such as poor performance due to extrapolation and undesired local minima. Consequently, we successfully create reliable and highly efficient configurations for metasurface color filters capable of producing exceptionally vivid colors that go beyond the sRGB gamut. Furthermore, our deep learning technique can be extended to design various pixellated metasurface configurations with different functionalities.

Nanoparticle Imprint Lithography: From Nanoscale Metrology to Printable Metallic Grids.

Large scale and low-cost nanopatterning of materials is of tremendous interest for optoelectronic devices. Nanoimprint lithography has emerged in recent years as a nanofabrication strategy that is high-throughput and has a resolution comparable to that of electron-beam lithography (EBL). It is enabled by pattern replication of an EBL master into polydimethylsiloxane (PDMS), that is then used to pattern a resist for further processing, or a sol-gel that could be calcinated into a solid material. Although the sol-gel chemistry offers a wide spectrum of material compositions, metals are still difficult to achieve. This gap could be bridged by using colloidal nanoparticles as resist, but deep understanding of the key parameters is still lacking. Here, we use supported metallic nanocubes as a model resist to gain fundamental insights into nanoparticle imprinting. We uncover the major role played by the surfactant layer trapped between nanocubes and substrate, and measure its thickness with subnanometer resolution by using gap plasmon spectroscopy as a metrology platform. This enables us to quantify the van der Waals (VDW) interactions responsible for the friction opposing the nanocube motion, and we find that these are almost in quantitative agreement with the Stokes drag acting on the nanocubes during nanoimprint, that is estimated with a simplified fluid mechanics model. These results reveal that a minimum thickness of surfactant is required, acting as a spacer layer mitigating van der Waals forces between nanocubes and the substrate. In the light of these findings we propose a general method for resist preparation to achieve optimal nanoparticle mobility and show the assembly of printable Ag and Au nanocube grids, that could enable the fabrication of low-cost transparent electrodes of high material quality upon nanocube epitaxy.

Enhanced Refractive Index Sensitivity through Combining a Sol-Gel Adsorbate with a TiO2 Nanoimprinted Metasurface for Gas Sensing.

We combine a gas-adsorbent microporous hybrid silica layer and a dense TiO2 Mie resonator array (metasurface), both obtained by sol-gel deposition and nanoimprint lithography, to form nanocomposite systems with high sensitivity for refractive index (RI) variations induced by gas adsorption. Using optical transduction based on direct specular reflection, we show spectral shifts of 4470 nm/RIU corresponding to 0.2 nm/ppm gas (air concentration) and reflection intensity changes of R* = 17 (R/RIU) and 0.55 × 10-3 R/ppm (air concentration). The metasurface is composed of hexagonally arranged TiO2 nanopillar arrays, whereas the surrounding sensitive material is a class II microporous hybrid silica, containing methyl and phenyl covalently bonded organic functions. This hybrid layer shows efficient adsorption capability of volatile organic molecules such as isopropanol, which is used to induce slight variations of RI around the TiO2 antennas. Specular reflectance variations at 45° incidence and refractive index measurements are performed using a spectroscopic ellipsometer. The presence of the titania metasurface enhances the signal by almost an order of magnitude with respect to the 2D counterpart (simulated as an effective medium approximation) and is attributed to the antenna effect, enhancing the interaction of the confined electromagnetic wave with the sensitive microporous medium. This sol-gel nanocomposite system presents many advantages such as high throughput and low-cost elaboration of elements and a high chemical, mechanical, and thermal resistance, ensuring high stability as a potential gas-sensitive nanocomposite layer for long periods. This work is a case study of improving the sensitivity of sol-gel gas-sensitive materials in optical transduction, which will be exploited in further works to develop artificial noses.

Quasi-Guided Modes in Titanium Dioxide Arrays Fabricated via Soft Nanoimprint Lithography.

Reversible quasi-guided modes (QGMs) are observed in titanium dioxide (TiO2) metasurface arrays fabricated via soft nanoimprint lithography. A TiO2 layer between the nanopillar array and the substrate can facilitate the propagation of QGMs. This layer is porous, allowing for the tuning of the layer properties by incorporating another material. The presence of the QGMs is strongly dependent on the refractive index of the TiO2 layer. QGMs are not supported if the refractive index of the porous TiO2 is too low. It is demonstrated that after depositing R6G on the array QGMs can be observed as very strong and narrow reflectance peaks and transmittance dips. Furthermore, as the second material can penetrate through the pores into the layer it can experience the regions of high field enhancement associated with the QGMs. These results are of interest for a wide range of applications including but not limited to sensing, nonlinear optics, and emission control.

Scalable Disordered Hyperuniform Architectures via Nanoimprint Lithography of Metal Oxides.

Fabrication and scaling of disordered hyperuniform materials remain hampered by the difficulties in controlling the spontaneous phenomena leading to this novel kind of exotic arrangement of objects. Here, we demonstrate a hybrid top-down/bottom-up approach based on sol-gel dip-coating and nanoimprint lithography for the faithful reproduction of disordered hyperuniform metasurfaces in metal oxides. Nano- to microstructures made of silica and titania can be directly printed over several cm2 on glass and on silicon substrates. First, we describe the polymer mold fabrication starting from a hard master obtained via spontaneous solid-state dewetting of SiGe and Ge thin layers on SiO2. Then, we assess the effective disordered hyperuniform character of master and replica and the role of the thickness of the sol-gel layer on the metal oxide replicas and on the presence of a residual layer underneath. Finally, as a potential application, we show the antireflective character of titania structures on silicon. Our results are relevant for the realistic implementation over large scales of disordered hyperuniform nano- and microarchitectures made of metal oxides, thus opening their exploitation in the framework of wet chemical assembly.

Porosimetry for Thin Films of Metal-Organic Frameworks: A Comparison of Positron Annihilation Lifetime Spectroscopy and Adsorption-Based Methods.

Thin films of crystalline and porous metal-organic frameworks (MOFs) have great potential in membranes, sensors, and microelectronic chips. While the morphology and crystallinity of MOF films can be evaluated using widely available techniques, characterizing their pore size, pore volume, and specific surface area is challenging due to the low amount of material and substrate effects. Positron annihilation lifetime spectroscopy (PALS) is introduced as a powerful method to obtain pore size information and depth profiling in MOF films. The complementarity of this approach to established physisorption-based methods such as quartz crystal microbalance (QCM) gravimetry, ellipsometric porosimetry (EP), and Kr physisorption (KrP) is illustrated. This comprehensive discussion on MOF thin film porosimetry is supported by experimental data for thin films of ZIF-8.

Following in Situ the Degradation of Mesoporous Silica in Biorelevant Conditions: At Last, a Good Comprehension of the Structure Influence.

Mesoporous silica nanoparticles (MSNs) have seen a fast development as drug delivery carriers thanks to their tunable porosity and high loading capacity. The employ of MSNs in biomedical applications requires a good understanding of their degradation behavior both to control drug release and to assess possible toxicity issues on human health. In this work, we study mesoporous silica degradation in biologically relevant conditions through in situ ellipsometry on model mesoporous nanoparticle or continuous thin films, in buffer solution and in media containing proteins. In order to shed light on the structure/dissolution relationship, we performed dissolution experiments far from soluble silicate species saturation. Via a complete decorrelation of dissolution and diffusion contributions, we proved unambiguously that surface area of silica vectors is the main parameter influencing dissolution kinetics, while thermal treatment and open mesoporous network architecture have a minor impact. As a logical consequence of our dissolution model, we proved that the dissolution lag-time can be promoted by selective blocking of the mesopores that limits the access to the mesoporous internal surface. This study was broadened by studying the impact of the organosilanes in the silica structure, of the presence of residual structuring agents, and of the chemical composition of the dissolution medium. The presence of albumin at blood concentration was found affecting drastically the dissolution kinetics of the mesoporous structure, acting as a diffusion barrier. Globally, we could identify the main factors affecting mesoporous silica materials degradation and proved that we can tune their structure and composition for adjusting dissolution kinetics in order to achieve efficient drug delivery.

Templated dewetting of single-crystal sub-millimeter-long nanowires and on-chip silicon circuits.

Large-scale, defect-free, micro- and nano-circuits with controlled inter-connections represent the nexus between electronic and photonic components. However, their fabrication over large scales often requires demanding procedures that are hardly scalable. Here we synthesize arrays of parallel ultra-long (up to 0.75 mm), monocrystalline, silicon-based nano-wires and complex, connected circuits exploiting low-resolution etching and annealing of thin silicon films on insulator. Phase field simulations reveal that crystal faceting and stabilization of the wires against breaking is due to surface energy anisotropy. Wires splitting, inter-connections and direction are independently managed by engineering the dewetting fronts and exploiting the spontaneous formation of kinks. Finally, we fabricate field-effect transistors with state-of-the-art trans-conductance and electron mobility. Beyond the first experimental evidence of controlled dewetting of patches featuring a record aspect ratio of [Formula: see text]1/60000 and self-assembled [Formula: see text]mm long nano-wires, our method constitutes a distinct and promising approach for the deterministic implementation of atomically-smooth, mono-crystalline electronic and photonic circuits.

Bimodal Porosity and Stability of a TiO2 Gig-Lox Sponge Infiltrated with Methyl-Ammonium Lead Iodide Perovskite.

We created a blend between a TiO2 sponge with bimodal porosity and a Methyl-Ammonium Lead Iodide (MAPbI3) perovskite. The interpenetration of the two materials is effective thanks to the peculiar sponge structure. During the early stages of the growth of the TiO2 sponge, the formation of 5-10 nm-large TiO2 auto-seeds is observed which set the micro-porosity (<5 nm) of the layer, maintained during further growth. In a second stage, the auto-seeds aggregate into hundreds-of-nm-large meso-structures by their mutual shadowing of the grazing Ti flux for local oxidation. This process generates meso-pores (10-100 nm) treading across the growing layer, as accessed by tomographic synchrotron radiation coherent X-ray imaging and environmental ellipsometric porosimetry. The distributions of pore size are extracted before (>47% V) and after MAPbI3 loading, and after blend ageing, unfolding a starting pore filling above 80% in volume. The degradation of the perovskite in the blend follows a standard path towards PbI2 accompanied by the concomitant release of volatile species, with an activation energy of 0.87 eV under humid air. The use of dry nitrogen as environmental condition has a positive impact in increasing this energy by ~0.1 eV that extends the half-life of the material to 7 months under continuous operation at 60 °C.

Pore Size-Dependent Structure of Confined Water in Mesoporous Silica Films from Water Adsorption/Desorption Using ATR-FTIR Spectroscopy.

The local structure of water on chemically and structurally different surfaces is a subject of ongoing research. In particular, confined spaces as found in mesoporous silica have a pronounced effect on the interplay between the adsorbate-adsorbate and adsorbate-surface interactions. Mid-infrared spectroscopy is ideally suited to quantitatively and qualitatively study such systems as the probed molecular vibrations are highly sensitive to intermolecular interactions. Here, the quantity and structure of water adsorbed from the gas phase into silica mesopores at different water vapor pressures was monitored using mid-infrared attenuated total reflection (ATR) spectroscopy. Germanium ATR crystals were coated with different mesoporous silica films prepared by evaporation-induced self-assembly. Quantitative analysis of the water bending vibration at 1640 cm-1 at varying vapor pressure allows for retrieving porosity and pore size distribution of the mesoporous films. The results were in excellent agreement with those obtained from ellipsometric porosimetry. In addition, different degrees of hydrogen bonding of water as reflected in the band position and shape of the stretching vibrations (3000-3800 cm-1) were analyzed and attributed to high-density, unordered bulk, low-density, and surface-induced ordered water. Thereby, the progression of surface-induced ordered water and bulk water as a function of water vapor pressure was studied for different pore sizes. Small pores of 5 nm diameter showed a number of two-ordered monolayers, whereas for pores >12 nm diameter, the number of ordered monolayers is significantly larger and agrees with the number observed on planar SiO2 surfaces.

Method To Detect Ethanol Vapor in High Humidity by Direct Reflection on a Xerogel Coating.

A simple double thin-film coating-based device is proposed to quantify the ethanol content in humid air featuring a 10 ppm resolution and spanning a dynamic range from 0 to 1000 ppm. The transduction involves the measurement of the direct optical reflection intensity, changing upon refractive index variations induced by water and ethanol adsorption within the coatings. The first thin-film coating is a microporous methyl-functionalized, silica xerogel material more sensitive to alcohol, and the second one is a microporous pure silica xerogel material more sensitive to water. The precision of the sensor is achieved through a mathematical treatment applied on the time resolved adsorption period. Reflection signals of both the ethanol- and water-sensitive coatings are taken into account in the treatment to correct for differences in ambient conditions (temperature, relative humidity, presence of volatile organic compounds) within the same chamber previous to data analysis, which corresponds to realistic operating conditions. As the adsorption mechanism is governed by molecular dynamic equilibrium, these sensors are fast and instantaneously regenerated in ambient air. The sensor is easy to assemble and was reusable for a period exceeding 1 year (maximal tested time).

Conductive-bridge memory cells based on a nanoporous electrodeposited GeSbTe alloy.

We report on the fabrication of memory devices based on a nanoporous GeSbTe layer electrodeposited inbetween TiN and Ag electrodes. It is shown that devices can operate along two distinct electrical modes consisting of a volatile or a non-volatile resistance switching mode upon appropriate preconditioning procedures. Based on electrical measurements conducted in both switching modes and physical analysis performed on a device after electrical stress, resistance switching is attributed to the formation/dissolution of a conductive filament from the Ag electrode into the GST layer whereas the volatile/non-volatile resistance switching is attributed to the presence of an interface layer between the GST and the Ag top electrode. Due to their simple, low-cost and low-temperature fabrication procedure, these devices could be advantageously exploited in flexible electronic applications or embedded into the back-end of line CMOS technology.

Dynamic Shaping of Femtoliter Dew Droplets.

Herein, we show that wetting properties such as giant wetting anisotropy and dynamic shaping can be observed when femtoliter (submicron scale) dew droplets are condensed on nanopatterned mildly hydrophilic surfaces. Large-scale, optically transparent, nanopatterned TiO2 surfaces were fabricated by direct nanoimprinting lithography of sol-gel-derived films. Square, infinitely elongated, or circular droplets were obtained with square, line, or concentric patterns, respectively, and were visualized in situ during formation and recession using optical microscopy and environmental scanning electronic microscopy. We first describe how extremely elongated droplets could form on mildly hydrophilic surfaces, naturally contaminated in real environmental conditions. In this configuration, the dew droplet shape can be dynamically and reversibly varied by controlling the out-of-equilibrium conditions associated with condensation/evaporation kinetics. As an example of the application, we propose a "morphological" sensor that exploits the shape of the dew droplets as a transduction mode for detecting organic vapors in the outer atmosphere. Importantly, this study is underlining that environmentally stable, purely hydrophilic surfaces can be smartly engineered to induce wetting phenomena at very small scale never observed so far for hydrophobic or heterogeneous surfaces. Our versatile approach based on nanoimprinted, transparent sol-gel films could open great perspectives for the implementation of environmentally stable, mildly hydrophilic materials for "dew engineering" applications such as open microfluidics, fuming for fingerprints, vapor sensing, or water harvesting on glass windows, for instance.

Environment-controlled sol-gel soft-NIL processing for optimized titania, alumina, silica and yttria-zirconia imprinting at sub-micron dimensions.

Metal oxide (MOX) surface nanopatterns can be prepared using Soft-Nano-Imprint-Lithography (soft-NIL) combined with sol-gel deposition processing. Even if sol-gel layers remain gel-like straight after deposition, their accurate replication from a mould remains difficult as a result of the fast evaporation-induced stiffening that prevents efficient mass transfer underneath the soft mould. The present work reports a detailed investigation of the role of the xerogel layer conditioning (temperature and relative humidity) prior to imprinting and its influence on the quality of the replication. This study is performed on four different systems namely titania, alumina, silica and yttria-stabilised zirconia. We demonstrate that the quality of the replica can be considerably improved without the use of sacrificial stabilising organic agents, but by simply applying an optimal aging at controlled temperature and relative humidity specific to each different reported MOX. In each case this condition corresponds to swelling the initial xerogels of around 30%vol by water absorption from humidity. We show that this degree of swelling represents the best compromise for sufficiently increasing the xerogel fluidity while limiting the shrinkage upon final thermal curing.

Full Investigation of Angle Dependence in Dip-Coating Sol-Gel Films.

Dip-coating is one of the most convenient methods used in laboratory and industry to deposit a solid layer onto a surface with a controlled thickness from a chemical solution. The present Article investigates the influence of the withdrawal speed on the film thickness and homogeneity with respect to the dipping angle ranging from 90° (conventional vertical configuration) to 1° (quasi-horizontal configuration). Several advantages were found in the latter extreme low-dipping angle conditions that are (i) an available wider range of thickness, (ii) the elimination of the perturbations/effects induced by evaporation, and (iii) the compatibility with large surface and single face deposition at high throughput and using a minimal amount of solution. One shows that experimental data follow the Landau-Levich model, modified by Tallmadge for angle dependence, only for intermediate regimes of speed. A maximal thickness limited by the physical-chemical characteristics of the initial solution is reached at high speeds while a minimal thickness, corresponding to a single layer of solute interacting with the substrate surface can be obtained at very low speeds.

Suppressing Structural Colors of Photocatalytic Optical Coatings on Glass: The Critical Role of SiO2.

The appearance of structural colors on coated-glass is a critical esthetical drawback toward industrialization of photocatalytic coatings on windows for architecture or automobile. Herein we describe a rational approach to suppress the structural color of mesoporous TiO2-based coatings preserving photoactivity and mechanical stiffness. Addition of SiO2 as third component is discussed. TixSi(1-x)O2 mesoporous coatings were fabricated by one-step liquid deposition process through the evaporation induced self-assembling and characterized by GI-SAXS, GI-WAXS, electron microscopies, and in situ Environmental Ellipsometry Porosimetry. Guided by optical simulation, we investigated the critical role of SiO2 on the optical responses of the films but also on the structural, mechanical, and photocatalytic properties, important requirements to go toward real applications. We demonstrate that adding SiO2 to porous TiO2 allows tuning and suppression of structural colors through refractive index matching and up to 160% increase in mechanical stiffening of the films. This study leads us to demonstrate an example of "invisible" coating, in which the light reflection is angle- and thickness-independent, and exhibiting high porosity, mechanical stiffness, and photoactivity.

Complex dewetting scenarios of ultrathin silicon films for large-scale nanoarchitectures.

Dewetting is a ubiquitous phenomenon in nature; many different thin films of organic and inorganic substances (such as liquids, polymers, metals, and semiconductors) share this shape instability driven by surface tension and mass transport. Via templated solid-state dewetting, we frame complex nanoarchitectures of monocrystalline silicon on insulator with unprecedented precision and reproducibility over large scales. Phase-field simulations reveal the dominant role of surface diffusion as a driving force for dewetting and provide a predictive tool to further engineer this hybrid top-down/bottom-up self-assembly method. Our results demonstrate that patches of thin monocrystalline films of metals and semiconductors share the same dewetting dynamics. We also prove the potential of our method by fabricating nanotransfer molding of metal oxide xerogels on silicon and glass substrates. This method allows the novel possibility of transferring these Si-based patterns on different materials, which do not usually undergo dewetting, offering great potential also for microfluidic or sensing applications.

Converting Water Adsorption and Capillary Condensation in Usable Forces with Simple Porous Inorganic Thin Films.

This work reports an innovative humidity-driven actuation concept based on conversion of chemical energy of adsorption/desorption using simple nanoporous sol-gel silica thin films as humidity-responsive materials. Bilayer-shaped actuators, consisting of a humidity-sensitive active nanostructured silica film deposited on a polymeric substrate (Kapton), were demonstrated as an original mean to convert water molecule adsorption and capillary condensation in usable mechanical work. Reversible solvation stress changes in silica micropores by water adsorption and energy produced by the rigid silica film contraction, induced by water capillary condensation in mesopores, were finely controlled and used as energy sources. The influence of the film nanostructure (microporosity, mesoporosity) and thickness and the polymeric substrate thickness on actuation force, on movement speed and on displacement amplitude are clearly evidenced and discussed. We show that the global mechanical response of such silica-based actuators can easily be adjusted to fabricate tailor-made actuation systems triggered by humidity variation. This study provides insight into hard ceramic stimulus-responsive materials that seem to be a promising alternative to traditional soft organic materials for surface-chemistry-driven actuation systems.